CN101248096A - Process for the copolymerization of propylene - Google Patents
Process for the copolymerization of propylene Download PDFInfo
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- CN101248096A CN101248096A CNA2006800210338A CN200680021033A CN101248096A CN 101248096 A CN101248096 A CN 101248096A CN A2006800210338 A CNA2006800210338 A CN A2006800210338A CN 200680021033 A CN200680021033 A CN 200680021033A CN 101248096 A CN101248096 A CN 101248096A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/00—Polymerisation catalysts
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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Abstract
A solution polymerization process comprising contacting under polymerization conditions propylene and at least ethylene or an alpha olefin of formula CH2=CHT wherein T is a C2-C20 alkyl radical, in the presence of a catalyst system obtainable by contacting: b) at least a metallocene compound of formula (I) b) alumoxane or a compound capable of forming an alkyl metallocene cation; and optionally c) an organo aluminum compound; wherein the groups R<1>R<4>, L, M and W are described in the text.
Description
The present invention relates to a kind of propylene of implementing in solution is CH with ethene at least or a kind of general formula
2(wherein T is C to=CHT
2-C
20The preparation method of the isotactic copolymer of alpha-olefin alkyl).Described method is implemented by using particular variety Metallocenyl catalyst system.
It is well known in the prior art using the method for metallocene catalyst system propylene copolymerization.The example of a series of solution polymerizations for example, has been described in EP629632.Yet the document has been described the catalyst system of the Metallocenyl of the two indenyls of a kind of bridge joint, and wherein indenyl only is substituted in 2 and 4 position.In addition, this polymerization result still can improve again.
WO03/050131 has described the metallocene compound of the two indenyls of a class bridge joint, and wherein the indenyl part is substituted on 2,4 and 5 position at least.In the document, used about 100 pages of examples for compounds of enumerating to comprise in the general formula, all these compounds all are the two indenyl metallocene compounds of bridge joint that replace in 2,4 and 5 position.WO03/050131 states that such metallocene compound can be used to comprise each polymerization process of solution polymerization, all is the slurry polymerisation method yet all embodiment relate to.
PCT/EP2004/013827 discloses the two indenyl metallocene compounds of a class, and wherein the indenyl part is substituted on 5 and 6 position by condensed ring.PCT/EP2004/013827 mainly concentrates on C
1Symmetrical structure does not clearly disclose C
2Symmetric compound.In other words, the document concentrates on and comprises two metallocene compounds with cyclopentadiene base section of different substitute modes.
Therefore need find a kind of can be with the catalyst system of produced in high yields high-molecular-weight propylene multipolymer, and it can use in solution polymerization process meeting under the industrialized temperature.
The objective of the invention is a kind of solution polymerization process, it is included in and makes propylene under a kind of existence of catalyst system and ethene or a kind of general formula are CH at least under polymerizing condition
2(wherein T is C to=CHT
2-C
20Alkyl) alpha-olefin contact, described catalyst system can obtain by making following component contact:
A) metallocene compound of at least a general formula (I);
B) aikyiaiurnirsoxan beta maybe can form the compound of alkyl metallocene cation; With optional
C) organo-aluminium compound;
Wherein in the metallocene compound of general formula (I):
M is selected from that those belong to the atom of the transition metal of 3 or 4 families or group of the lanthanides or actinium series in the periodic table of elements; Preferred M is zirconium, titanium or hafnium;
X, identical or different each other, be hydrogen atom, halogen atom, R, OR, OR ' O, OSO
2CF
3, OCOR, SR, NR
2Or PR
2Group, wherein R is straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl; Randomly contain the heteroatoms that belongs to periodic table of elements 13-17 family; R ' is C
1-C
20Alkylidene group, C
6-C
20Arylidene, C
7-C
20Alkyl arylene or C
7-C
20Aryl alkylene; Preferred X is hydrogen atom, halogen atom, OR ' O or R group; More preferably X is chlorine or methyl;
L is selected from C
1-C
20Alkylidene group, C
3-C
20Ring alkylidene group, C
6-C
20Arylidene, C
7-C
20Alkyl arylene or C
7-C
20The divalent abutment of aryl alkylene randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Perhaps it is to contain the nearly silicylene of 5 Siliciumatoms; Preferred L is Si (R
11)
2, R wherein
11Be straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl; More preferably L is Si (CH
3)
2Or SiPh
2
R
1Be the C of straight chain
1-C
40Alkyl, randomly contain the heteroatoms that belongs to periodic table of elements 13-17 family, for example methyl or ethyl or the alpha-branched aryl or aralkyl that contains 2 to 20 carbon atoms and randomly contain O, N, S, P and Se atom, especially O, N, S atom, for example 2 (5-Me-thiophenyls) or 2 (5-Me-furyls); Preferred R
1It is straight chain C
1-C
20Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R
1Be the C of straight chain
1-C
10Alkyl; More preferably R
1Be methyl or ethyl;
R
2And R
3, identical or different each other, be C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family, perhaps R
2And R
3Be the part that is fused to the 4-7 unit ring of indenyl part phenyl ring, described ring randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; The valence link of each atom that forms described ring is by R
18Group replaces; This represents that it is by R
18Group is saturated, wherein R
18, identical or different each other, be hydrogen atom or C
1-C
20Alkyl; Preferred R
18Be hydrogen atom or straight chain or branching, cyclic or acyclic C
1-C
20Alkyl, C
2-C
20Alkenyl, C
2-C
20Alkynyl, C
6-C
20Aryl, C
7-C
20Alkylaryl or C
7-C
20Aralkyl, described group randomly contain the one or more heteroatomss that belong to periodic table of elements 13-17 family; More preferably R
18Be C hydrogen atom or straight chain or branching
1-C
20Alkyl; More preferably R
18Be hydrogen atom or methyl or ethyl; Described ring can be saturated or it can comprise two keys; Preferred R
2And R
3, identical or different each other, be straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family, perhaps R
2And R
3It is the part of 5 or 6 yuan of rings; Described ring randomly contains the heteroatoms that belongs to periodic table of elements 13-16 family, preferred elements periodictable 15-16 family; The valence link of each atom that forms described ring is by R
18Group replaces; As mentioned above; Preferred R
2And R
3Be C
1-C
20Alkyl or form the saturated 3-7 unit ring of condensation together;
R
4Be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R
4Be hydrogen atom or straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl, described group randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R
4Be hydrogen atom or C
1-C
10Alkyl or C
6-C
40Aryl;
W is 5 or 6 yuan of rings of aromatics, and it can contain the heteroatoms that belongs to periodic table of elements 15-16 family; The valence link of each atom of described ring is replaced by hydrogen atom or it can be randomly by R
5Group replaces, wherein R
5, identical or different each other, be C
1-C
40Alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R
5Be straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family;
Preferred W is selected from following general formula (Wa), (Wb) and part (Wc):
Wherein on behalf of this part, * connect the position of the indenyl part of general formula (I) compound;
R
6, R
7, R
8, R
9And R
10, identical or different each other, be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R
6, R
7, R
8, R
9And R
10Be hydrogen atom or straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl, described group randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family;
Z
1Be nitrogen-atoms or CR
10Group; Z
2Be nitrogen-atoms or CR
6Group; Z
3Be nitrogen-atoms or CR
7Group; Z
4Be nitrogen-atoms or CR
8Group; Z
5Be nitrogen-atoms or CR
9Group; Condition is Z
1, Z
2, Z
3, Z
4And Z
5In to be no more than 2 groups are nitrogen-atoms, preferred Z
1, Z
2, Z
3, Z
4And Z
5In to be no more than a group be nitrogen-atoms;
Z
6Be Sauerstoffatom, sulphur atom, NR
13Group or CR
13Group; Z
7Be Sauerstoffatom, sulphur atom, NR
14Group or CR
14Group; Z
8Be Sauerstoffatom, sulphur atom, NR
15Group or CR
15Group; Z
9Be Sauerstoffatom, sulphur atom, NR
16Group or CR
16Group; Z
10Be nitrogen-atoms or the carbon atom that is bonded to the indenyl part of general formula (I) structure; Condition is Z
6, Z
7, Z
8, Z
9Or Z
10In to be no more than a group be sulphur atom, Sauerstoffatom or be selected from NR
13, NR
14, NR
15, NR
16Nitrogen-containing group atom and nitrogen-atoms;
R
13, R
14, R
15And R
16, identical or different each other, be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R
6, R
7, R
8, R
9And R
10Be hydrogen atom or straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl, described group randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; More preferably R
6, R
7, R
8, R
9And R
10Be hydrogen atom, C
1-C
40Alkyl or C
6-C
40Aryl;
In the part of general formula (Wa), in a preferred embodiment, R
7Be C
1-C
40Alkyl, the preferably C of branching
1-C
40Alkyl, for example tertiary butyl, more preferably R
7Be that wherein the alpha position carbon atom is the C of the branching of tertiary carbon atom
1-C
40Alkyl, and R
6, R
8, R
9And R
10It is hydrogen atom;
In a preferred embodiment, R
10And R
8Be C
1-C
40Alkyl, preferably they are C of straight chain
1-C
40Alkyl, for example methyl, and R
7And R
9It is hydrogen group;
In a preferred embodiment, R
6, R
7And R
8Be C straight chain or branching
1-C
40Alkyl, for example methyl or the tertiary butyl, and R
10And R
9It is hydrogen atom;
In a preferred embodiment, R
6, R
7, R
8, R
9And R
10It is hydrogen atom;
In the part of general formula (Wb), in a preferred embodiment, Z
1Be nitrogen-atoms, and Z
2, Z
3, Z
4And Z
5Be respectively CR
6, CR
7, CR
8And CR
9, R wherein
6, R
7, R
8And R
9Implication as mentioned above; In a preferred embodiment, Z
3Be nitrogen-atoms, and Z
1, Z
2, Z
4And Z
5Be respectively CR
10, CR
6, CR
8And CR
9, R wherein
10, R
6, R
8And R
9Implication as mentioned above; In a preferred embodiment, Z
2Be nitrogen-atoms, and Z
1, Z
3, Z
4And Z
5Be respectively CR
10, CR
7, CR
8And CR
9, R wherein
10, R
7, R
8And R
9Implication as mentioned above;
In the part of general formula (Wc), in a preferred embodiment, Z
6Be Sauerstoffatom, sulphur atom, NR
16Group; Preferably it is sulphur atom or NR
16R wherein
16C preferably
1-C
40Alkyl; More preferably Z
6It is sulphur atom; And Z
7, Z
8, Z
9And Z
10Be respectively CR
14, CR
15, CR
16And carbon atom, wherein R
14Be hydrogen atom or C
1-C
40Alkyl, for example methyl or ethyl; R
15And R
16Be hydrogen atom or C
1-C
40Alkyl.
The compound of the preferred general formula of one class (I) has general formula (IIa), (IIb) or (IIc):
Wherein M, L, X, R
1, R
4, R
6, R
7, R
8, R
9And R
10Implication as mentioned above, and R
11And R
12, identical or different each other, be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R
11And R
12Be hydrogen atom or straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, described group randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; More preferably R
11And R
12Be hydrogen atom or C
1-C
10Alkyl, for example methyl or ethyl.
The metallocene compound of preferred formula (I) has C
2Symmetry.The symmetrical kind of metallocene can be published in Chemical Reviews at Resconi etc., and 2000, Vol.100 finds in the document of No.41263, and the document is incorporated herein as a reference.
The metallocene compound that is preferred in the method for the present invention is their racemize or the racemic form of class.The racemic form of racemize or class has been described in PCT/EP2005/052688.
Following is the examples for compounds with general formula (I).
Me
2Si (6-Me-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (6,8-Me2-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si[6-Me-4-(4-t-BuPh)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl]
2ZrCl
2,
Me
2Si[6,8-Me2-4-(4-t-BuPh)-1,2,3,5-tetrahydrochysene-s-and indenes 7-yl]
2ZrCl
2,
Me
2Si[6-Me-4-(2-MePh)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl]
2ZrCl
2,
Me
2Si[6,8-Me2-4-(2-MePh)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl]
2ZrCl
2,
Me
2Si[1,1,3,3,6-Me5-4-(2-MePh)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl]
2ZrCl
2,
Me
2Si[6-Me-4-(2,5-Me2Ph)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl]
2ZrCl
2,
Me
2Si[6-Me-4-(4-phenylbenzene)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl]
2ZrCl
2,
Me
2Si (1,1,3,3,6-Me5-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si[1,1,3,3,6-Me5-4-(4-t-BuPh)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl]
2ZrCl
2,
Me
2Si (2,2,, 6-Me3-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (2-Me-4-Ph-1H-encircles five [b] naphthalene-1-yl)
2ZrCl
2,
Me
2Si (2,5,8-Me3-4-Ph-1H-encircles five [b] naphthalene-1-yl)
2ZrCl
2,
Me
2Si (2-Me-4-Ph-5,6,7,8-tetrahydrochysene-1H-encircles five [b] naphthalene-1-yl)
2ZrCl
2,
Me
2Si (2,6-Me2-4-Ph-5H-1-sulphur-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (2,3,6-Me3-4-Ph-5H-1 sulphur-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (2,6-Me2-4-(4-t-BuPh)-5H-1 sulphur-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (2,3,6-Me3-4-(4-t-BuPh)-5H-1-sulphur-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (2-Me-4-Ph-1,5,6,7,8,9-six hydrogen ring seven [f] indenes-1-yls)
2ZrCl
2,
Me
2Si (6-Me-4-(2-benzothienyl)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (6-Me-4-(2-(5-thiotolene base))-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (6-Me-4-(2-(5-methyl furan base))-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (6-Me-4-(4-pyridyl)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
C
2H
4(6-Me-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
C
2H
4(6,8-Me2-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Ph
2Si (6-Me-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Ph
2Si (6,8-Me2-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl)
2ZrCl
2,
Me
2Si (6-Me-4-(2-(5-thiotolene base))-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl) (6-Me-4-Ph-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl) ZrCl
2,
Me
2Si (6,8-Me2-4-phenyl-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl) (6-Me-4-(4-t-BuPh)-1,2,3,5-tetrahydrochysene-s-and indenes-7-yl) ZrCl
2,
With they corresponding dimethyl derivatives.
Method of the present invention is preferably under 60 ℃ of-200 ℃ of temperature, more preferably implementing under 80 ℃ of-120 ℃ of temperature under 70 ℃ of-150 ℃ of temperature and more preferably.
Be used for can considering that according to the aikyiaiurnirsoxan beta of the inventive method straight chain, branching or cyclic contains the compound of at least one following type group:
Wherein substituting group U is identical or different, as above-mentioned definition.
Especially, in the situation of straight chain compound, can use the aikyiaiurnirsoxan beta of following general formula:
N wherein
1Be 0 or the integer of 1-40, and substituting group U such as above-mentioned definition; Perhaps in the situation of ring compound, can use the aikyiaiurnirsoxan beta of following general formula:
N wherein
2Be the integer of 2-40, and substituting group U such as above-mentioned definition.
The example that is fit to the aikyiaiurnirsoxan beta of use according to the present invention is methylaluminoxane (MAO), four-(isobutyl-) aikyiaiurnirsoxan beta (TIBAO), four-(2,4,4-trimethylammonium-amyl group) aikyiaiurnirsoxan beta (TIOAO), four-(2, the 3-dimethylbutyl) aikyiaiurnirsoxan beta (TDMBAO) and four-(2,3,3-trimethylammonium butyl) aikyiaiurnirsoxan beta (TTMBAO).
Useful especially promotor be wherein alkyl described in WO99/21899 and the WO01/21674 and aryl have special branched pattern those.
The non-limiting instance that can provide the aluminum compound of suitable aikyiaiurnirsoxan beta (b) with water reaction described in WO99/21899 and the WO01/21674 is:
Three (2,3,3-trimethylammonium-butyl) aluminium, three (2,3-dimethyl-hexyl) aluminium, three (2,3-dimethyl-butyl) aluminium, three (2,3-dimethyl-amyl group) aluminium, three (2,3-dimethyl-heptyl) aluminium, three (2-methyl-3-ethyl-amyl group) aluminium, three (2-methyl-3-ethyl-hexyl) aluminium, three (2-methyl-3-ethyl-heptyl) aluminium, three (2-methyl-3-propyl group-hexyl) aluminium, three (2-ethyl-3-methyl-butyl) aluminium, three (2-ethyl-3-methyl-amyl group) aluminium, three (2,3-diethyl-amyl group) aluminium, three (2-propyl group-3-methyl-butyl) aluminium, three (2-sec.-propyl-3-methyl-butyl) aluminium, three (2-isobutyl--3-methyl-amyl group) aluminium, three (2,3,3-trimethylammonium-amyl group) aluminium, three (2,3,3-trimethylammonium-hexyl) aluminium, three (2-ethyls-3,3-dimethyl-butyl) aluminium, three (2-ethyls-3,3-dimethyl-amyl group) aluminium, three (2-sec.-propyls-3,3-dimethyl-butyl) aluminium, three (2-trimethyl silyl-propyl group) aluminium, three (2-methyl-3-phenyl-butyl) aluminium, three (2-ethyl-3-phenyl-butyl) aluminium, three (2,3-dimethyl-3-phenyl-butyl) aluminium, three (2-phenyl-propyl group) aluminium, three [2-(4-fluoro-phenyl)-propyl group] aluminium, three [2-(4-chloro-phenyl)-propyl group] aluminium, three [2-(3-sec.-propyl-phenyl)-propyl group] aluminium, three (2-phenyl-butyl) aluminium, three (3-methyl-2-phenyl-butyl) aluminium, three (2-phenyl-amyl group) aluminium, three [2-(phenyl-pentafluoride base)-propyl group] aluminium, three [2,2-phenylbenzene-ethyl] aluminium and three [2-phenyl-2-methyl-propyl group] aluminium, and one of them alkyl by the displaced corresponding compounds of hydrogen atom and one of them or two alkyl by isobutyl-displaced those.
In above-mentioned aluminum compound, trimethyl aluminium (TMA), triisobutyl aluminium (TIBA), three (2,4,4-trimethylammonium-amyl group) aluminium (TIOA), three (2, the 3-dimethylbutyl) aluminium (TDMBA) and three (2,3,3-trimethylammonium butyl) aluminium (TTMBA) are preferred.
The non-limiting instance that can form the compound of alkyl metallocene cation is a general formula D
+E
-Compound, D wherein
+Be Br_nsted acid, can provide proton and irreversibly react with the substituent X of the metallocene of general formula (I), and E
-Be the paired negatively charged ion, it can be stablized and is derived from two kinds of compound reactive activity catalyzer kinds, and it is enough unstable, thereby can remove by olefinic monomer.Preferably, negatively charged ion E
-Comprise one or more boron atoms.More preferably, negatively charged ion E
-Be Formula B Ar
4 (-)Negatively charged ion, wherein substituent A r can be identical or different, it is an aryl, for example phenyl, phenyl-pentafluoride base or two (trifluoromethyl) phenyl.Four-phenyl-pentafluoride ylboronic acid ester is particularly preferred compound, as described in WO91/02012.In addition, Formula B Ar
3Compound can eligibly use.For example in the International Patent Application WO 92/00333 this compounds is being described.Other example that can form the compound of alkyl metallocene cation is Formula B Ar
3The compound of P, wherein P is that replace or unsubstituted pyrryl.These compounds have been described in WO01/62764.The compound of boracic atom can be according to the explanation quilt load eligibly of DE-A-19962814 and DE-A-19962910.The compound of all these boracic atoms can with boron to the mol ratio of the metal of metallocene be included in about 1: 1 to about 10: 1, preferred 1: 1 to 2: 1, more preferably from about be used for 1: 1 time.
General formula D
+E
-The non-limiting instance of compound be:
Four (phenyl-pentafluoride base) aluminic acid tributyl ammonium,
Four (three fluoro aminomethyl phenyls) boric acid tributyl ammonium,
Four (4-fluoro phenyl) boric acid tributyl ammonium,
Four (phenyl-pentafluoride base) boric acid N, the N-dimethyl benzyl ammonium,
Four (phenyl-pentafluoride base) boric acid N, N-dimethyl hexyl ammonium,
Four (phenyl-pentafluoride base) boric acid N, N-dimethyl puratized agricultural spray,
Four (phenyl-pentafluoride base) aluminic acid N, N-dimethyl puratized agricultural spray,
Four (phenyl-pentafluoride base) boric acid N, the N-dimethyl benzyl ammonium,
Four (phenyl-pentafluoride base) boric acid N, N-dimethyl hexyl ammonium,
Four (phenyl-pentafluoride base) boric acid two (propyl group) ammoniums,
Four (phenyl-pentafluoride base) boric acid two (cyclohexyl) ammoniums,
Four (phenyl-pentafluoride base) boric acid triphenylcarbenium,
Four (phenyl-pentafluoride base) aluminic acid triphenylcarbenium,
Four (phenyl-pentafluoride base) boric acid ferrocene (ferrocenium),
Four (phenyl-pentafluoride base) aluminic acid ferrocene (ferrocenium),
Four (phenyl-pentafluoride base) boric acid triphenylcarbenium and
Four (phenyl-pentafluoride base) boric acid N, N-dimethyl puratized agricultural spray.
Spendable general formula D has been described in WO04/005360, WO02/102811 and WO01/62764 according to the present invention
+E
-Other example of compound.
As compound c) organo-aluminium compound be aforesaid general formula H
jAlU
3-jOr H
jAl
2U
6-jThose.
Catalyst system of the present invention can contact in solvent with the promotor that is fit to by the metallocene that makes general formula (I) and prepare.Promotor is the reaction product of methylaluminoxane and triisobutyl aluminium preferably.
Catalyzer of the present invention can be according to PCT/EP2005/002479 by toluene distillation or do not carry out this distillation by following described technology and prepare.
Catalyzer of the present invention also can load on the inert support.This by with metallocene compound a) or itself and components b) reaction product or first components b) then metallocene compound a) deposit on the inert support and realize.This carrier can be the porous solid, for example the polymer powder of talcum, sheet silicate, inorganic oxide or fine dispersion (as polyolefine).The inorganic oxide that is fit to can find in the oxide compound of the periodic table of elements 2,3,4,5,13,14,15 and 16 family's elements.Preferably the example as the oxide compound of carrier comprises the oxide compound of silicon-dioxide, aluminum oxide and blended calcium, aluminium, silicon, magnesium or titanium elements and mixture, magnesium halide, vinylbenzene/divinyl benzene copolymer, polyethylene or the polypropylene of corresponding oxide.
Can use separately or with other inorganic oxide that above-mentioned preferred oxides carrier is united use be for example MgO, ZrO
2, TiO
2Or B
2O
3
The operable carrier that one class is fit to be the porous organic carrier by group functionalization with active hydrogen atom constitute those.Particularly suitable is that wherein organic carrier is those of partial cross-linked styrene polymer.This class carrier has been described in European application EP-633272.
The another kind of inert support that is particularly suitable for the present invention's use is the especially poly porous prepolymer of polyolefine.
The another class inert support of suitable use is the porous magnesium halide according to the present invention, those as describing in the International Application No. WO 95/32995.
The solid support material that uses preferably has 10-1000m
2The median size of the specific surface area of/g, the pore volume of 0.1-5ml/g and 1-500 μ m.Preferred vector has 50-500m
2The median size of the specific surface area of/g, the pore volume of 0.5-3.5ml/g and 5-350 μ m.Special preferred vector has 200-400m
2The median size of the specific surface area of/g, the pore volume of 0.8-3.0ml/g and 10-300 μ m.
Can heat-treat inorganic carrier, for example remove the moisture of absorption.This drying treatment usually 80-300 ℃, preferably 100-200 ℃ of enforcement; preferably under reduced pressure and/or rare gas element (as nitrogen) protection, implement in the drying under 100-200 ℃, perhaps can calcine inorganic carrier down to obtain desirable solid structure and/or to set desirable OH concentration at 200-1000 ℃ on its surface.This carrier also can be used conventional siccative such as metal alkylide class, preferred alkyl aluminium class, chlorosilane or SiCl
4, or other methylaluminoxane carry out chemical treatment.The treatment process that is fit to has for example been described in WO00/31090.
Inorganic carrier material also can be a chemical modification.For example, with (NH
4)
2SiF
6Handle silica gel and make the silica gel surface fluorination, the silane treatment silica gel of the group of perhaps nitrogenous with comprising, fluorine or sulphur makes the silica gel surface obtain corresponding modification.
Also can use for example polyolefin powder of fine dispersion (as polyethylene, polypropylene or polystyrene) of organic support material, and remove moisture, solvent residue or other impurity of attachment removal by suitable purifying and drying operation before also preferred the use.Also can use functionalized polymer support, for example based on the carrier of vinylbenzene, via its functional group for example carboxyl or hydroxyl, fixing at least a catalyst component.Loading to the solid chemical compound that obtains on the carrier by the catalyst system with target of the present invention can unite use with the alkylaluminium cpd that adds later like this, perhaps can react in advance with water before uniting use if desired.
For purpose of the present invention, term " solution polymerization " is illustrated in that polymkeric substance is dissolved in polymerisation medium fully under the polymerization temperature that is adopted, and concentration range is 5～50 weight %.
In order to make polymkeric substance be dissolved in polymerisation medium fully, can use the monomer mixture in the presence of inert solvent.This solvent can be aliphatics or cycloaliphatic hydro carbons for example hexane, heptane, octane-iso, Permethyl 99A., hexanaphthene and methylcyclohexane.Also can use mineral spirits or hydrogenant diesel oil distillate.Also can use aromatic hydrocarbon based for example toluene.The preferred solvent that uses is hexanaphthene and methylcyclohexane.Propylene content in the mixture can change according to the content of hope final comonomer in multipolymer and the relative reactivity ratio of comonomer.Propylene content in the polymerisation medium liquid phase is preferably 5 weight %-60 weight %; 20 weight %-50 weight % more preferably.
The temperature range that is used for polymerization process of the present invention is 60 ℃-200 ℃, preferred 80 ℃-150 ℃, and more preferably 89 ℃-120 ℃.
Can use hydrogen to regulate the molecular weight of the polymkeric substance of acquisition effectively.Preferably, the concentration of hydrogen is 1ppm-1000ppm, is preferably 2ppm-300ppm.
The ratio of comonomer changes accordingly according to relative comonomer reactivity ratio in desirable final copolymer and the catalyst system.
The technician can select propylene and the monomeric ratio of copolymerization, to obtain desirable multipolymer.
The multipolymer that the method according to this invention obtains especially has those of high comonomer content, is very sticking, and this makes when being difficult to produce in industrial equipments during the enforcement polymerization process in slurry or in the gas phase, because can silt up in reactor.On the contrary, when implement be the method for solution polymerization the time, this problem can be avoided.
The method according to this invention, propylene is with ethene or a kind of general formula are CH at least
2(wherein T is C to=CHT
2-C
20Alkyl) alpha-olefin contact.General formula is CH
2The example of the alpha-olefin of=CHT is 1-butylene, 1-amylene, 4-methyl 1-amylene, 1-hexene, 1-octene, 4,6-dimethyl-1-heptene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene and 1-icosa alkene.The preferred comonomer that uses is ethene, 1-butylene and 1-hexene.
Comprise nearly 95 moles of % propylene derived units in the multipolymer that obtains according to the present invention.The content of preferred propylene derived unit is 30 moles of % to 91 mole of %.More preferably the content of propylene derived unit is 70 moles of % to 91 mole of %.
Mixture that can be by using different metallocene compounds or by according to polymerization temperature and/or concentration of molecular weight regulator and/or monomer concentration and different several stages implement polymerization and change molecular weight distribution.In addition, use two kinds of different metallocene compounds to implement polymerization process can to prepare the polymkeric substance of giving wide fusing point by uniting.
The polymkeric substance that obtains according to the inventive method can further contain the nearly non-conjugated diene hydrocarbon of 20 moles of %.The non-conjugated diene hydrocarbon can be straight chain, side chain or the cyclic hydrocarbon dienes hydrocarbon with 6 to 20 carbon atoms.The example of the non-conjugated diene hydrocarbon that is fit to is:
The acyclic dienes of-straight chain, for example 1,4-hexadiene and 1,6-octadiene;
The acyclic dienes of-side chain, 5-methyl isophthalic acid for example, 4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1, the isomer of 7-octadiene and blended dihydro myrcene and dihydro ocimene;
-monocyclic alicyclic diene, for example 1,1,1,5-cyclooctadiene and 1,5-encircle 12 carbon diene;
The alicyclic multiviscosisty of-polycyclic and cyclic diolefine bridge joint, for example tetrahydro-indenes, methyltetrahydro indenes, Dicyclopentadiene (DCPD), two ring-(2,2,1)-heptan-2,5-diene; With
-alkenyl, alkylidene group, cycloalkenyl and ring alkylidene group norbornylene, for example 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene, 5-cyclohexylene-2-norbornylene, 5-vinyl-2-norbornylene and norbornadiene.
Preferred diolefine is 1,4-hexadiene (HD), 5-ethylidene 2-norbornylene (ENB), 5-vinylidene-2-norbornylene (VNB), 5-methylene-2-norbornene (MNB) and Dicyclopentadiene (DCPD) (DCPD).Particularly preferred diolefine is 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
When existing, the non-conjugated diene hydrocarbon preferably with 0.1 mole of % to about 20 moles of %, preferred 0.5 mole of % to 15 mole of %, more preferably 0.5 mole of % to 7 mole of %, also more preferably the amount of 0.5 mole of % to 3 mole of % is incorporated in the polymkeric substance.If desired, can sneak into simultaneously more than a kind of diolefine, for example HD and ENB, its total amount of sneaking into is in the restriction of afore mentioned rules.
Therefore, another target of the present invention is a kind of solution polymerization process, and it is included under a kind of existence of catalyst system and makes propylene under polymerizing condition, and ethene or a kind of general formula are CH at least
2(wherein T is C to=CHT
2-C
20Alkyl) alpha-olefin contacts with the non-conjugated diene hydrocarbon, and described catalyst system can obtain by making following component contact:
A) metallocene compound of at least a general formula (I);
B) aikyiaiurnirsoxan beta maybe can form the compound of alkyl metallocene cation; With optional
C) organo-aluminium compound.
The following example is illustrative rather than definitive thereof the present invention.
Embodiment
All chemical reagent must be used standard Schlenk technical finesse.
Methylaluminoxane (MAO) obtains from Albemarle, 30% (w/w) toluene solution, and by this use.
Pure triisobutyl aluminium (TIBA) former state is used.
Permethyl 99A. is carried out purifying by alumina, make moisture content be lower than 10ppm.
Obtain 110g/L TIBA/ Permethyl 99A. solution by mixing said ingredients.
Polymer analysis
I.V. under 135 ℃ in tetraline THN intrinsic viscosity.
DSC. on the Perkin Elmer DSC-7 calorimeter that Pyris 1 software is installed, in solid state properties (FE-PPC) laboratory, careful especially ground accurately calibration under the fusing point of indium and zinc when determining the baseline of required precision in advance uses dsc (DSC) to measure the fusing point (T of polymkeric substance
m).For calorimetric research, the preparation of sample is implemented by cutting into fritter with cutting machine.The weight of the sample in each DSC crucible remains on 6.0 ± 0.5mg.
The sample of weighing is sealed in the aluminium pot, and is heated to 180 ℃ with 10 ℃/minute speed.Thermal spike is taken Tm (I) as.Keep sample 180 ℃ of temperature 5 minutes, make all crystallites melt fully, be cooled to 20 ℃ with 10 ℃/minute speed then.After 20 ℃ down keep 2 minutes, with 10 ℃/minute speed control second-heating samples to 180 ℃.In second time heat-processed, take thermal spike as melt temperature (Tm (II)), and peak area is taken melting enthalpy (Δ H as
f).
13C-NMR measures
Use by the Bruker DPX400 spectrometer that 100.61MHz operates down
13C-NMR analyzes chemical constitution and the comonomer distribution of studying multipolymer.Measure the sym.-tetrachloroethane solution of sample 8% (w/v), spend pulses at 120 ℃ of following records with 90
13C-NMR spectrum, and between pulse and CPD, delay time 12 seconds to eliminate
1H-
13The C coupling.In the 32K data point, store about 1K transient state with 6000Hz spectrum window.S under 29.9ppm
δ δPeak (according to the term of reference 1) is used as internal reference (internal reference).Calculate reactivity ratio r according to reference 1 by tlv triple (triads)
1* r
2Product.Measure multipolymer composition and tlv triple distribution according to reference 2.
Reference 1:Carman, C.J.; Harrington, R.A.; Wilkes, CE.Macromolecules1977,10,563
Reference 2:Kakugo, M.; Naito, Y.; Mizunuma, K.Macromolecules1982,15,1150.
Dichloro zirconium (IV) (A-1) to prepare racemize dimetylsilyl two (2-methyl-4-(4-tert-butyl-phenyl)-1,5,6,7-tetrahydrochysene-s-and indenes-1-yl) according to EP05102189
Prepare racemize-dimetylsilyl two (2-methyl-4-phenyl-indenyl) dichloro zirconium (racemize-μ-{ two-[η according to USP5786432
5-2-methyl-4-phenyl-indenes-1-yl] dimethylsilane two bases } dichloro zirconium (IV)) (C-1).
According to WO98/40331 (embodiment 65) preparation racemize-dimetylsilyl two (2-methyl-4-(right-tert-butyl-phenyl)-indenyl) dichloro zirconium (racemize-Me
2Si (2-Me-4 (4-t-BuPh) Ind)
2ZrCl
2) (C-2).
The preparation catalyst system
Catalyst system A-0C
(Sylopol 948 for filling 3.6g silica in filtering table processing strainer up
TM), and be suspended in the 20mL toluene.Under agitation be metered into 8.8mL30%MAO (methylaluminoxane) concentration solution, add speed and should make internal temperature be no more than 35 ℃.After the stirring, with low speed restir 1 hour, the rotary processing strainer made its filtering table down, and filtering suspension liquid at first under atmospheric pressure, adopts the 3bar nitrogen pressure then.Walk abreast with handling solid support material, be placed in the 118mg A-1 among the 1.1mL 30% concentration MAO in reaction vessel, stirred solution 1 hour makes it leave standstill then 30 minutes.Then solution is joined in the pretreated solid support material that is suspended in the 20mL toluene.Finish after the adding stirred suspension 15 minutes.The nitrogen that applies 3bar is pressed, and solution is drained.Drying solid under vacuum at last.
Catalyst system A-1C
A-1/MAO∶TIBA 2∶1(Al/Zr＝400)
14.6mL TIBA/ Permethyl 99A. solution (110g/L) is mixed with 3.4mL MAO/ toluene solution (Albemarle 30%wt/wt), and obtaining the MAO/TIBA mol ratio is 2: 1.At room temperature stirred solution is 30 minutes.Then, 50mg A-1 is dissolved in the solution.Organic solution does not demonstrate the vestige of any residual solids.
With the final solution of 8mL dilution with toluene, make concentration reach 100g/L (1.92g A-1/L).Catalyst system C-1C
C-1/MAO∶TIBA 2∶1(Al/Zr＝400)：
9.5mL TIBA/ Permethyl 99A. solution (110g/L) and 2.7mL MAO/ toluene solution (Albemarle 30%wt/wt, 12.8mmol MAO) are mixed, and obtaining the MAO/TIBA mol ratio is 2.4: 1.At room temperature stirred solution is 30 minutes.Then, 25mg C-1 is dissolved in the solution.Solution does not demonstrate the vestige of any residual solids.With the final solution of 5.1mL dilution with toluene, make concentration reach 105g/L (1.45g metallocene/L).
Catalyst system C-2C
C-2/MAO∶TIBA 2∶1(Al/Zr＝400)
8.1mL TIBA/ Permethyl 99A. solution (110g/L) and 1.9mL MAO/ toluene solution (Albemarle 30%wt/wt, 9mmol MAO) are mixed, and obtaining the MAO/TIBA mol ratio is 2: 1.At room temperature stirred solution is 30 minutes.Then, 25mg C-2 is dissolved in the solution.Solution does not demonstrate the vestige of any residual solids.With the final solution of 4.4mL dilution with toluene, make concentration reach 100g/L (1.74g metallocene/L).
Aggregation test
Embodiment 1
To be furnished with agitator of magnetic drive and the stainless steel cylinder of 35-mL and with the stainless steel pressure kettle that is used for the 4.4L strap clamp cover that temperature controlled thermostatted links to each other with the Al (i-Bu) that is dissolved in hexane
3Solution is cleaned in advance, and dry under 50 ℃ in nitrogen gas stream.
With 6mmol A1 (i-Bu)
3(being dissolved in the 100g/L solution of hexane), 958g hexanaphthene, 45g ethene and 489g propylene feed are to reactor, to obtain the liquid composition that respective liquid under 90 ℃, 22bar-g pressure consists of the ethylene/propene of 7/93 weight %.
The catalyst system A-1C (1.92mg metallocene/mL solution) that 1mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 1 hour of 18/82 weight %, to keep the pressure of 22bar-g: consume 79.6g propylene and 18.9g ethene.
Pressure in the pressure kettle is reduced to 20bar, open bottom drain valve, multipolymer is discharged in the cylinder of steel of the heating that 70 ℃ of water are housed.Stop heating, inject the nitrogen gas stream of 0.5bar-g pressure this jar.After being cooled to room temperature, opening cylinder of steel and collect wet polymer.Under 70 ℃ of reduced pressure in baking oven the dry wet polymkeric substance.Aggregated data is listed in table 1.
Embodiment 2
Repeat the process of embodiment 1, inject 958g hexanaphthene, 41g ethene and 651g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 29bar-g pressure consists of the ethylene/propene of 5/95 weight %.
The catalyst system A-1C (1.92mg metallocene/mL solution) that 1mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 14/86 weight %, to keep the pressure of 29bar-g: consume 98.6g propylene and 16.3g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
Embodiment 3
Repeat the process of embodiment 1, inject 958g hexanaphthene, 64g ethene and 473g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 23bar-g pressure consists of the ethylene/propene of 10/90 weight %.
The catalyst system A-1C (1.92mg metallocene/mL solution) that 1mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 20/80 weight %, to keep the pressure of 23bar-g: consume 30.9g propylene and 7.5g ethene.The results are shown in table 1
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
The comparative example 4
Repeat the process of embodiment 1, inject 958g hexanaphthene, 31g ethene and 500g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 22bar-g pressure consists of the ethylene/propene of 5/95 weight %.
The catalyst system C-1C (1.48mg metallocene/mL solution) that 2mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 19/81 weight %, to keep the pressure of 22bar-g: consume 22.6g propylene and 5.3g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
The comparative example 5
Repeat the process of embodiment 1, inject 958g hexanaphthene, 50g ethene and 484g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 23bar-g pressure consists of the ethylene/propene of 8/92 weight %.
The catalyst system C-1C solution (1.48mg metallocene/mL solution) that 3mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 18/82 weight %, to keep the pressure of 23bar-g: consume 72.6g propylene and 14.9g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
The comparative example 6
Repeat the process of embodiment 1, inject 958g hexanaphthene, 64g ethene and 473g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 26bar-g pressure consists of the ethylene/propene of 10/90 weight %.
The catalyst system C-1C (1.48mg metallocene/mL solution) that 4mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 20/80 weight %, to keep the pressure of 26bar-g: consume 186.5g propylene and 45.9g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
The comparative example 7
Repeat the process of embodiment 1, inject 958g hexanaphthene, 31g ethene and 500g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 21bar-g pressure consists of the ethylene/propene of 5/95 weight %.
The catalyst system C-2C solution (1.74mg metallocene/mL solution) that 4mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 11/89 weight %, to keep the pressure of 21bar-g: consume 33.7g propylene and 4.1g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
The comparative example 8
Repeat the process of embodiment 1, inject 958g hexanaphthene, 50g ethene and 484g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 24bar-g pressure consists of the ethylene/propene of 8/92 weight %.
The catalyst system C-1C solution (1.74mg metallocene/mL solution) that 4mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 16/84 weight %, to keep the pressure of 24bar-g: consume 31.2g propylene and 5.9g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
The comparative example 9
Repeat the process of embodiment 1, inject 958g hexanaphthene, 64g ethene and 473g propylene, to obtain the liquid composition that respective liquid under 90 ℃, 26bar-g pressure consists of the ethylene/propene of 10/90 weight %.
The catalyst system C-2C solution (1.74mg metallocene/mL solution) that 4mL contains the catalyst/co-catalyst mixture is expelled in the pressure kettle with the 4mL hexanaphthene by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 20/80 weight %, to keep the pressure of 26bar-g: consume 86.5g propylene and 21.6g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
Embodiment 10
To be furnished with agitator of magnetic drive and the stainless steel cylinder of 35-mL and with the stainless steel pressure kettle that is used for the 4.4L strap clamp cover that temperature controlled thermostatted links to each other with the Al (i-Bu) that is dissolved in hexane
3Solution is cleaned in advance, and dry under 50 ℃ in nitrogen gas stream.
With 6mmol Al (i-Bu)
3(being dissolved in the 100g/L solution of hexane), 950g hexanaphthene, 70.5g ethene and 469g propylene feed are to reactor, to obtain the liquid composition that respective liquid under 90 ℃, 26.85bar-g pressure consists of the ethylene/propene of 13/87 weight %.
115mg catalyst A-0C is expelled in the pressure kettle with the 5mL Permethyl 99A. by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 20/80 weight %, to keep the pressure of 26.85bar-g: consume 118.5g propylene and 30.6g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 1.
Table 1
| Embodiment | Catalyst system | T pol℃ | Active kg/ (gmet*h) § | I.V.dl/g | C2 contmol％ | r1r2 |
| 1 | A-1C | 95 | 272 | 1.61 | 19.9 | 1.37 |
| 2 | A-1C | 95 | 347 | 1.44 | 14.6 | 1.67 |
| 3 | A-1C | 90 | 200 | 2.08 | 30.2 | 1.60 |
| 4 * | C-1C | 92 | 16 | 1.25 | 10.7 | 2.78 |
| 5 * | C-1C | 90 | 38 | 1.23 | 17.2 | 2.18 |
| 6 * | C-1C | 95 | 85 | 1.05 | 24.6 | 2.01 |
| 7 * | C-2C | 90 | 26 | 1.29 | 11.6 | 2.52 |
| 8 * | C-2C | 90 | 36 | 116 | 17.9 | 2.34 |
| 9 * | C-2C | 92 | 74 | 1.26 | 23.8 | 2.01 |
| 10 | A-0C | 95 | 214 | 1.20 | 33.9 | 1.52 |
*The comparative example
N.a. can not obtain
The § activity per hour provides with kg multipolymer/every gram metallocene.
Can clearly draw the polymerization activity of the employed general formula of the inventive method (I) metallocene compound employed metallocene compound in the comparative example under the same polymeric condition from table 1.Simultaneously, the molecular weight of the polymkeric substance of the inventive method acquisition also is higher than the comparative example.When the metallocene compound of general formula (I) during, also can keep higher activity by load.
Catalyst system A-1Cl
A-1/MAO∶TIBA 2∶1(AITOT/Zr＝600)
(Albemarle30%wt/wt 24mmolMAO) mixes, and obtaining the MAO/TIBA mol ratio is 2: 1 with 5mL MAO/ toluene solution with 21.8mL TIBA/ Permethyl 99A. solution (110g/L).At room temperature stirred solution is 30 minutes.Then, 49.6mg A-1 is dissolved in the solution, and with resulting green/to be diluted to concentration with the 11.7mL Permethyl 99A. be 100g TOT/L and 1.29g metallocene/L to brown suspension.After at room temperature stirring was spent the night, mixture became dark orange solution.
Aggregation test
Embodiment 11
To be furnished with agitator of magnetic drive and the stainless steel cylinder of 35-mL and with the stainless steel pressure kettle that is used for the 4.4L strap clamp cover that temperature controlled thermostatted links to each other with the Al (i-Bu) that is dissolved in hexane
3Solution is cleaned in advance, and dry under 50 ℃ in nitrogen gas stream.
With 6mmol Al (i-Bu)
3(being dissolved in the 100g/L solution of hexane), 720g hexanaphthene, 35g ethene and 654g propylene feed are to reactor, to obtain the liquid composition that respective liquid under 100 ℃, 33bar-g pressure consists of the ethylene/propene of 0.04 (wt/wt).
1mL catalyst A-1Cl is expelled in the pressure kettle with the 5mL Permethyl 99A. by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 10/90 weight %, to keep the pressure of 33bar-g: consume 171.3g propylene and 19.7g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 2.
Embodiment 12
To be furnished with agitator of magnetic drive and the stainless steel cylinder of 35-mL and with the stainless steel pressure kettle that is used for the 4.4L strap clamp cover that temperature controlled thermostatted links to each other with the Al (i-Bu) that is dissolved in hexane
3Solution is cleaned in advance, and dry under 50 ℃ in nitrogen gas stream.
With 6mmol Al (i-Bu)
3(being dissolved in the 100g/L solution of hexane), 715g hexanaphthene, 61g ethene and 631g propylene and 50mL hydrogen are fed in the reactor, to obtain the liquid composition that respective liquid under 100 ℃, 35bar-g pressure consists of the ethylene/propene of 0.08 (wt/wt).
1mL catalyst A-1Cl is expelled in the pressure kettle with the 5mL Permethyl 99A. by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 17/83 weight %, to keep the pressure of 35bar-g: consume 109.3g propylene and 22.8g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 2.
Embodiment 13
To be furnished with agitator of magnetic drive and the stainless steel cylinder of 35-mL and with the stainless steel pressure kettle that is used for the 4.4L strap clamp cover that temperature controlled thermostatted links to each other with the Al (i-Bu) that is dissolved in hexane
3Solution is cleaned in advance, and dry under 50 ℃ in nitrogen gas stream.
With 6mmol Al (i-Bu)
3(being dissolved in the 100g/L solution of hexane), 715g hexanaphthene, 61g ethene and 631g propylene and 500mL hydrogen are fed in the reactor, to obtain the liquid composition that respective liquid under 100 ℃, 35bar-g pressure consists of the ethylene/propene of 0.08 (wt/wt).
1mL catalyst A-1Cl is expelled in the pressure kettle with the 5mL Permethyl 99A. by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 17/83 weight %, to keep the pressure of 35bar-g: consume 238g propylene and 48.6g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 2.
Embodiment 14
To be furnished with agitator of magnetic drive and the stainless steel cylinder of 35-mL and with the stainless steel pressure kettle that is used for the 4.4L strap clamp cover that temperature controlled thermostatted links to each other with the Al (i-Bu) that is dissolved in hexane
3Solution is cleaned in advance, and dry under 50 ℃ in nitrogen gas stream.
With 6mmol Al (i-Bu)
3(being dissolved in the 100g/L solution of hexane), 676g hexanaphthene, 72g ethene and 647g propylene feed are to reactor, to obtain the liquid composition that respective liquid under 100 ℃, 38bar-g pressure consists of the ethylene/propene of 0.09 (wt/wt).
1.5mL catalyst A-1Cl is expelled in the pressure kettle with the 5mL Permethyl 99A. by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 21/79 weight %, to keep the pressure of 38bar-g: consume 96.1g propylene and 25.7g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 2.
Embodiment 15
To be furnished with agitator of magnetic drive and the stainless steel cylinder of 35-mL and with the stainless steel pressure kettle that is used for the 4.4L strap clamp cover that temperature controlled thermostatted links to each other with the Al (i-Bu) that is dissolved in hexane
3Solution is cleaned in advance, and dry under 50 ℃ in nitrogen gas stream.
With 6mmol Al (i-Bu)
3(being dissolved in the 100g/L solution of hexane), 859g hexanaphthene, 53g ethene and 508g propylene feed are to reactor, to obtain the liquid composition that respective liquid under 120 ℃, 37bar-g pressure consists of the ethylene/propene of 0.09 (wt/wt).
1.5mL catalyst A-1Cl is expelled in the pressure kettle with the 5mL Permethyl 99A. by stainless steel cylinder.
Continuous feeding ethylene/propylene is the mixture 30 minutes of 17/83 weight %, to keep the pressure of 37bar-g: consume 144.6g propylene and 29.7g ethene.
According to the process that first embodiment describes multipolymer is discharged.
Aggregated data is listed in table 2.
Table 2
| Embodiment | T pol℃ | Active kg/ (gmet*30min) § | I.V.dl/g | C2 contmol％ | r1r2 |
| 11 | 100 | 247 | 1.43 | 13.0 | 1.4 |
| 12 | 100 | 147 | 1.95 | 24.7 | 1.4 |
| 13 | 100 | 258 | 1.22 | 22.6 | 1.5 |
| 14 | 100 | 265 | 1.91 | 29.2 | 1.4 |
| 15 | 120 | 195 | 1.15 | 31.7 | 1.2 |
The § activity provided with kg multipolymer/every gram metallocene in per 30 minutes.
Claims (11)
1. solution polymerization process, it is included under a kind of existence of catalyst system, makes propylene and ethene or a kind of general formula are CH at least under polymerizing condition
2The alpha-olefin contact of=CHT, wherein T is C
2-C
20Alkyl, described catalyst system can obtain by making following component contact:
A) metallocene compound of at least a general formula (I)
B) aikyiaiurnirsoxan beta maybe can form the compound of alkyl metallocene cation;
Wherein in the metallocene compound of general formula (I):
M is selected from the atom that those belong to the transition metal of 3 or 4 families in the periodic table of elements or group of the lanthanides or actinium series; X, identical or different each other, be hydrogen atom, halogen atom, R, OR, OR ' O, OSO
2CF
3, OCOR, SR, NR
2Or PR
2Group, wherein R is straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl; Randomly contain the heteroatoms that belongs to periodic table of elements 13-17 family; And R ' is C
1-C
20Alkylidene group, C
6-C
20Arylidene, C
7-C
20Alkyl arylene or C
7-C
20Aryl alkylene;
L is selected from C
1-C
20Alkylidene group, C
3-C
20Ring alkylidene group, C
6-C
20Arylidene, C
7-C
20Alkyl arylene or C
7-C
20The divalent abutment of aryl alkylene randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family; Perhaps it is to contain the nearly silicylene of 5 Siliciumatoms;
R
1Be the C of straight chain
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family, for example methyl or ethyl or the alpha-branched aryl or aralkyl that contains 2 to 20 carbon atoms and randomly contain O, N, S, P and Se atom;
R
2And R
3, identical or different each other, be C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family, perhaps R
2And R
3It is the part that is fused to the 4-7 unit ring of indenyl part phenyl ring; Described ring randomly contains the heteroatoms that belongs to periodic table of elements 13-16 family; The valence link of each atom that forms described ring is by R
18Group is saturated, wherein R
18, identical or different each other, be hydrogen atom or C
1-C
40Alkyl;
R
4Be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family;
W is 5 or 6 yuan of rings of aromatics, and it can contain the heteroatoms that belongs to periodic table of elements 13-16 family; The valence link of each atom of described ring is replaced by hydrogen atom or it can be randomly by R
5Group replaces, wherein R
5, identical or different each other, be C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family.
2. according to the process of claim 1 wherein that described catalyst system further comprises c) organo-aluminium compound.
3. according to the method for claim 1 or 2, M is zirconium, titanium or hafnium in the compound of its formula of (I); X is hydrogen atom, halogen atom, OR ' O or R group; L is Si (R
11)
2, R wherein
11Be straight chain or branching, cyclic or acyclic C
1-C
40Alkyl, C
2-C
40Alkenyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkylaryl or C
7-C
40Aralkyl; R
1Be C
1-C
10Alkyl.
4. according to each method of claim 1 to 3, R in the compound of its formula of (I)
2And R
3It is the part that is fused to the 5-6 unit ring of indenyl part phenyl ring; Described ring is by R
18Group replaces, wherein R
18Be C hydrogen atom or straight chain or branching
1-C
20Alkyl, R
4Be hydrogen atom, C
1-C
10Alkyl or C
6-C
40Aryl.
5. according to each method of claim 1-4, W is selected from following general formula (Wa), (Wb) and part (Wc) in the compound of its formula of (I):
Wherein on behalf of this part, * be keyed to the position of the indenyl part of general formula (I) compound;
R
6, R
7, R
8, R
9And R
10, identical or different each other, be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family;
Z
1Be nitrogen-atoms or CR
10Group; Z
2Be nitrogen-atoms or CR
6Group; Z
3Be nitrogen-atoms or CR
7Group; Z
4Be nitrogen-atoms or CR
8Group; Z
5Be nitrogen-atoms or CR
9Group; Condition is Z
1, Z
2, Z
3, Z
4And Z
5In to be no more than 2 groups are nitrogen-atoms;
Z
6Be Sauerstoffatom, sulphur atom, NR
13Group or CR
13Group; Z
7Be Sauerstoffatom, sulphur atom, NR
14Group or CR
14Group; Z
8Be Sauerstoffatom, sulphur atom, NR
15Group or CR
15Group; Z
9Be Sauerstoffatom, sulphur atom, NR
16Group or CR
16Group;
Z
10Be nitrogen-atoms or the carbon atom that is keyed to indenyl part in general formula (I) structure; Condition is Z
6, Z
7, Z
8, Z
9Or Z
10In to be no more than a group be sulphur atom, Sauerstoffatom or be selected from NR
13, NR
14, NR
15, NR
16Nitrogen-containing group and nitrogen-atoms;
R
13, R
14, R
15And R
16, identical or different each other, be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family.
6. according to each method of claim 1-5, the compound of its formula of (1) has general formula (IIa), (IIb) or (IIc):
Wherein M, L, X, R
1, R
4, R
10, R
6, R
7, R
8, R
14, R
15And R
16And R
9Implication such as claim 1-7 described in, and R
11And R
12, identical or different each other, be hydrogen atom or C
1-C
40Alkyl, described alkyl randomly contains the heteroatoms that belongs to periodic table of elements 13-17 family.
7. according to each method of claim 1-6, it is implemented under 60 ℃ of-200 ℃ of temperature.
8. according to each method of claim 1-7, wherein polymerisation medium is the liquid monomer mixture in the presence of aliphatics or cycloaliphatic varsol.
9. according to each method of claim 1-8, wherein propylene and ethene, 1-butylene or 1-hervene copolymer.
10. according to each method of claim 1-9, wherein in the presence of the described catalyst system of claim 1, under polymerizing condition, propylene is with ethene or a kind of general formula are CH at least
2The alpha-olefin of=CHT contacts with a kind of non-conjugated diene hydrocarbon, and wherein T is C
2-C
20Alkyl.
11. according to each method of claim 1-10, wherein said method is implemented in the presence of hydrogen.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05105137.3 | 2005-06-13 | ||
| EP05105137 | 2005-06-13 | ||
| US60/690,629 | 2005-06-15 |
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| Publication Number | Publication Date |
|---|---|
| CN101248096A true CN101248096A (en) | 2008-08-20 |
Family
ID=39947895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800210338A Pending CN101248096A (en) | 2005-06-13 | 2006-06-07 | Process for the copolymerization of propylene |
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| Country | Link |
|---|---|
| US (1) | US20090286946A1 (en) |
| EP (1) | EP1891123B1 (en) |
| JP (1) | JP2008544003A (en) |
| KR (1) | KR20080024128A (en) |
| CN (1) | CN101248096A (en) |
| AU (1) | AU2006259143A1 (en) |
| BR (1) | BRPI0613343A2 (en) |
| ES (1) | ES2692449T3 (en) |
| RU (1) | RU2008101445A (en) |
| WO (1) | WO2006134046A1 (en) |
| ZA (1) | ZA200710389B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666605A (en) * | 2009-12-22 | 2012-09-12 | 博里利斯股份公司 | Catalysts |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE445650T1 (en) | 2004-05-04 | 2009-10-15 | Basell Polyolefine Gmbh | METHOD FOR PRODUCING ATACTIC 1-BUTENE POLYMERS |
| US7868197B2 (en) | 2005-12-14 | 2011-01-11 | Exxonmobil Chemical Patents Inc. | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
| JP5295098B2 (en) * | 2006-04-21 | 2013-09-18 | バーゼル・ポリオレフィン・ゲーエムベーハー | Method for producing ethylene copolymer |
| US7812104B2 (en) | 2008-01-18 | 2010-10-12 | Exxonmobil Chemical Patents Inc. | Production of propylene-based polymers |
| JP5966321B2 (en) * | 2010-11-19 | 2016-08-10 | 日本ポリプロ株式会社 | Metallocene complex and olefin polymerization method |
| WO2013007664A1 (en) | 2011-07-08 | 2013-01-17 | Borealis Ag | Heterophasic copolymers |
| JP5880000B2 (en) * | 2011-12-14 | 2016-03-08 | 日本ポリプロ株式会社 | Metallocene complex and olefin polymerization method |
| JP6015306B2 (en) * | 2012-09-28 | 2016-10-26 | 日本ポリエチレン株式会社 | Metallocene compound, olefin polymerization catalyst component and olefin polymerization catalyst containing the same, and method for producing olefin polymer using the olefin polymerization catalyst |
| ES2674576T3 (en) * | 2012-12-21 | 2018-07-02 | Borealis Ag | Catalyst |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0552945B1 (en) * | 1992-01-23 | 1997-05-07 | Mitsui Petrochemical Industries, Ltd. | Process for the preparation of polyolefin |
| TW294669B (en) | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
| US7232871B2 (en) * | 1997-08-12 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
| DE19806918A1 (en) * | 1998-02-19 | 1999-08-26 | Aventis Res & Tech Gmbh & Co | Catalyst system for the production of olefin polymers, especially polypropylene |
| CN100575324C (en) * | 1999-12-23 | 2009-12-30 | 巴塞尔聚烯烃有限公司 | Transistion metal compound, ligand system, catalyst system and in the polyreaction of alkene and the purposes in the copolyreaction |
| US6376407B1 (en) * | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
| SG147306A1 (en) * | 2001-11-06 | 2008-11-28 | Dow Global Technologies Inc | Isotactic propylene copolymers, their preparation and use |
| DE10158656A1 (en) * | 2001-11-30 | 2003-06-26 | Basell Polyolefine Gmbh | Organo transition metal compound, biscyclopentadienyl ligand system, catalyst system and process for making polyolefins |
| ATE423784T1 (en) * | 2003-05-28 | 2009-03-15 | Basell Polyolefine Gmbh | BISINDENYL-ZIRCONIUM COMPLEXES FOR OLEFIN POLYMERIZATION |
| WO2005023889A1 (en) * | 2003-09-11 | 2005-03-17 | Basell Polyolefine Gmbh | Multistep process for preparing heterophasic propylene copolymers |
| JP5525680B2 (en) * | 2003-11-14 | 2014-06-18 | エクソンモービル・ケミカル・パテンツ・インク | Propylene-based elastomer, its product and its production method |
| DE10358082A1 (en) * | 2003-12-10 | 2005-07-14 | Basell Polyolefine Gmbh | Organometallic transition metal compound used in catalyst system for preparation of polyolefins, uses biscyclopentadienyl ligand systems in its preparation |
| WO2006065844A2 (en) * | 2004-12-16 | 2006-06-22 | Exxonmobil Chemical Patents Inc. | Process for producing substituted metallocene compounds for olefin polymerization |
| RU2410388C2 (en) | 2005-03-18 | 2011-01-27 | Базелль Полиолефине Гмбх | Metallocene compounds |
| ATE526337T1 (en) * | 2006-03-17 | 2011-10-15 | Basell Polyolefine Gmbh | METALLOCENE COMPOUNDS |
| JP2010500418A (en) * | 2006-04-21 | 2010-01-07 | バーゼル・ポリオレフィン・ゲーエムベーハー | Process for producing ethylene propylene copolymer |
| JP5295098B2 (en) * | 2006-04-21 | 2013-09-18 | バーゼル・ポリオレフィン・ゲーエムベーハー | Method for producing ethylene copolymer |
-
2006
- 2006-06-07 RU RU2008101445/04A patent/RU2008101445A/en not_active Application Discontinuation
- 2006-06-07 US US11/922,047 patent/US20090286946A1/en not_active Abandoned
- 2006-06-07 CN CNA2006800210338A patent/CN101248096A/en active Pending
- 2006-06-07 BR BRPI0613343-6A patent/BRPI0613343A2/en not_active Application Discontinuation
- 2006-06-07 AU AU2006259143A patent/AU2006259143A1/en not_active Abandoned
- 2006-06-07 EP EP06763558.1A patent/EP1891123B1/en active Active
- 2006-06-07 JP JP2008516281A patent/JP2008544003A/en active Pending
- 2006-06-07 KR KR1020077029151A patent/KR20080024128A/en not_active Application Discontinuation
- 2006-06-07 WO PCT/EP2006/062964 patent/WO2006134046A1/en active Application Filing
- 2006-06-07 ES ES06763558.1T patent/ES2692449T3/en active Active
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666605A (en) * | 2009-12-22 | 2012-09-12 | 博里利斯股份公司 | Catalysts |
| CN102666605B (en) * | 2009-12-22 | 2014-08-06 | 博里利斯股份公司 | Catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080024128A (en) | 2008-03-17 |
| WO2006134046A1 (en) | 2006-12-21 |
| ES2692449T3 (en) | 2018-12-03 |
| JP2008544003A (en) | 2008-12-04 |
| ZA200710389B (en) | 2008-10-29 |
| EP1891123A1 (en) | 2008-02-27 |
| RU2008101445A (en) | 2009-07-20 |
| BRPI0613343A2 (en) | 2011-01-04 |
| EP1891123B1 (en) | 2018-08-29 |
| AU2006259143A1 (en) | 2006-12-21 |
| US20090286946A1 (en) | 2009-11-19 |
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